Dyestuffs containing both azo-chromophores and quinone chromophores



DYESTUFFS CONTAINING BOTH AZO-CHROMO- PHORES AND QUINONE CHROMOPHORES No Drawing. Filed Jan. 22, 1957, Ser. No. 635,081

Claims priority, application Switzerland Jan. 27, 1956 Claims. (Cl. 260-153) This invention provides new dyestuffs, which contain in which n represents a whole number up to 3, R and R each represent a benzene radical, X represents an amino a bridge bound to R in meta-position to the azo linkage, Y represents the radical of a heterocyclic keto-methylene compound which is bound to the azo linkage in a position vicinal to a keto group, Z represents a sulfonic acid group or a hydrogen atom, and A represents a halogen atom or an -NH group or a radical bound to the carbon atom directly or through an oxygen or nitrogen bridge.

The invention also provides a process for the manufacture of the dyestuffs ofthe above Formula'2, wherein a dior a trihalogen-1,3,5-triazine is condensed on the.

one hand with an anthraquinone dyestufi of the formula r J Z son:

in which n and Z have the meanings given above, and on the other hand with a monoazo-dyestuff of the formula linkage, the halogen atom present in the obtained products of condensation being, if desired, replaced by an NH -group or by an organic radical.

dyestufi of the Formula 3.

As anthraquinone dyestuffs of the above kind which are used as starting materials in the present invention there may be mentioned more especially those which contain in the benzene nucleus R an amino groupcapable of being acylated, and especially an NH group. This amino group may be present in the meta-position or advantageously in' para-position to the NH group,

both azo-chromophores and quinone chromophores, and 15 -,2:3:8-trisu'lf'onic acid, 1 amino 4 (3-aminophenylwhich, like the dyestufi of the formula amino)-anthraquinone-2:4'-disulfonic acid, and also those a llVHz O HO sour I C-NH N-NC I N l NHONHC CNH SOsH 0H: /N c i V 1 a C1 7 i correspond to the general formula 30 containing a single sulfonic acid group, such as l-amino- (2) NH: 4-(4' or 3-aminophenylamino )-anthraquinone-Z-sulfonic C0 acid, 1-arnino-4-(3'-amino-4- or -6-methylphenylamino)- 0 A anthraquinone-Z-sulfbnic acid, 1- amino-4-(4-amino-3'- Z V l methylphenylamino)anthraquinone 2 sulfonic acid, 1- 35 amino-4%3-aminor4:6'-dimethylphenylarnino) anthra- N quinone 2 sulfonic acid, I1-amino-4-(4'-aminophenyl L amino) -anthraquinone-3'-sulfonic acid diethylamide-Z- k k sulfdnic acid and 1-amino-4-(4-aminophenylamino)- anthraquinone-3-methylsulfone-2-sulfonic acid. Orr-1H2n-l 40 As monoazo-dyestufis of the above Formula 4 there group. One mol of such an amino-azo-dyestufi may be' condensed first with 1 mol of cyanuric chloride or with 1 mol of a dihalogen-triazine of the formula A(|J (Iii-Halogen lIalogen in which A represents'an -NH group or an organic radical not of dyestuifcharacter, advantageously containing at most 12 carbon atoms, which is bound to the triazine nucleus directly or through an -O-- or --NH- bridge, and then with one mol of an anthraquinone The dihalogen-triazines of the above constitution can be made by methods in themselves known from cyanuric halides, such as cyanuric bromide or cyanuric chloride,

by reacting, for example, 1 mol of cyanuric chloride with 1 mol of an aminoor hydroxy-compound not having the character of a dyestuif. As such compounds there may be used ammonia, aliphatic'or aromatic hydroxy-compounds, such as methyl alcohol, ethyl alcohol or butyl alcohol, phenol, ortho-, metaor para-cresol, 4-secondarybutyl-phenol, 4-tertiary amyl-phenol, dialkyl-phenols,

3 para-chlorophenol and especially organic nitrogen compounds such as methylamine, dimethylamine, ethylamine, diethylarnine, isopropylamine, butylamine, hexylamine, phenylarnine, tolylamine, 4-chlorophenylamine, N-methylphenylamine or cyclohexylamine, and also p-chlorethylamine, methoxy-ethylamine, 'y-methoxy-propylamine or ethanolarnine. Suitable dihalogen-triazines of the above Formula 6 can also be obtained by methods in themselves known from 1 mol of cyanuric chloride and Intel of an alkyl-, cycloalkyl-, aralkyl-, or aryl-magnesium-halide.

The condensation .of the resulting triazine dyestuffs containing mobile halogen atoms with the anthraqui none dyestuffs is carried out advantageously in the presence of an acid-binding agent such as sodium acetate, sodium hydroxide, or sodium carbonate and advantageously in an aqueous medium.

The invention also provides a modification of the aforesaid process for producing the dyestufis of the Formula 2, wherein an anthraquinone dyestufi of the Formula 3 is condensed. with a cyanuric halide, especially cyanuric chloride, or with a dihalogen-triazine of the Formula 6 in the molecular ratio 1:1, and the condensation product so obtained is further condensed with 1 molecular propor tion of a dyestufi of the Formula 4.

When the condensation product so obtained still con-,

in which Z represents a sulfonic acid group or a hydrogen atom, A represents a chlorine atom or a substituent containing at most 12 carbon atoms which is bound to the triazine ring directly or advantageously through a nitrogen bridge, and Y represents the radical of barbituric acid or of a 3-methyl-5-pyrazolone bound in the 4-position to the azo linkage.

The dyestulis of this invention are suitable for dyeing or printing a very wide variety of materials, such as polyhydroxylated textile materials, for example, of polyvinyl alcohol or of natural or regenerated cellulose, and nitrogenous textile materials such as silk, leather and above all wool, and also synthetic fibers of superpolyamides or superpolyurethanes. When the starting materials are so chosen that the dyestuif produced contains one or at most two sulfonic acid groups, the dyestufis are suitable espe cially for dyeing nitrogenous textile materials from neutral or weakly acid baths, advantageously an acetic acid bath, of which the pH value is within the range of 5-7, and those dyestufis of the invention which contain more than two sulfonic acid groups and a halogen atom in the triazine nucleus are especially suitable'for dyeing cotton and polyhydroxylated materials. The latter dyestuffs, which contain a halogenated triazine nucleus and more than two sulfonic acid groups, can be applied to the fiber "to be dyed by the direct dyeing method or by the printing of so-called padding process and fixed on the fiber the character, of a dyestuli which are referred to above in connection with the preparation of the dihalogen-triazines of the Formula 6.

All the condensations are advantageously carried out at a pH value within the range of 5- 7. Depending onthe starting materials used it may be of advantage to raise the pH value'somewhat from stage to stage. It isgenerally desirable to maintain the pH-value asconstant as possibledtriiiig each stage, and this can be successfully carried out by continuously controlling and neutralizing the'hydrohalic acid liberated, for example, by means of 'an' alkali carbonate or alkali hydroxide.

I The present invention thus'provides interalia dyestuffs of the formula in which Y is the radical of barbituric acid or the radical of a 3-methyl-5-pyrazolone bound to the azo linkage in the 4-position, A is a lower hydrocarbon radical containfonic acid groups.

Especially valuable and easily accessibleare those dyestufis of the Formula 2 which correspond to the-formula by alkaline treatment. The dyeings and prints produced by these methods are distinguished by the especially good purity of their tints, by a good fastness to light and by excellent properties of wet fastness.

The following examples illustrate the invention, the parts and percentages being'by weight, unless otherwise stated:

Example I 8.18 parts of 1-amino-4-(4'-aminophenylamino)-anthraquinone-Z-sulfonic acid are dissolved in 200'parts of water with the addition of 0.9 part of sodium hydroxide and 1.1 parts of sodium carbonate at 40 C. Into the resulting solution are introduced 9.8 parts of the dyestufl of the formula v in the form of an aqueous paste of about 25% strength.

The reaction mixture is stirred for. 30 minutes at.35-.40

C. and for-SO minutes at 45-50 -C. The whole is. then lieated to C. The resulting dyestuif is filtered' ofi at that temperature and washed with 150 parts of sodium chloride solution of 2% strength. When dry it is a dark powder which dissolves in water with a green coloration and dyes wool from a neutral or weakly acetic acid bath clear green tints.

The dyestuff obtained as described above, advantageously without being dried, is boiled under reflux with 1000 parts of water and 3.8 parts of aniline, for 6 hours. After the addition of ,parts of-a saturatedasolution of sodium chloride the'mixtnreis stirred for-15 minutes. The dyestufi, whichprecipitates almost completely, is vliltered ofi while hot. When dry it is a dark powder which.

dissolves in water 'with'a greencoloration and dyes-wool from a neutral 'orwveaklyacetic acid bath clearigreen "tints. 'j"

The :azo dyestuffof the"a'bove' formula used as starting material can be prepared, forexamplens follows:

' 18.5 parts of cyanuric chloridearesuspended' iri parts of ice water, and 29.7 parts of a suspension of the dyestufi of the formula ENG-80:13

separated in the acid state (prepared by coupling diazotized l-acetylamino-3-aminobenzene-4-sulfonic acid with 3-methyl-5-pyrazolone followed by hydrolysis of the acetylamino group) in 400 parts of water. There are introduced dropwise into the resulting yellow suspension in the course of 3 hours at 2-5 C., 10.6 parts of sodium carbonate dissolved in 100 parts of water. The color of the suspension shifts towards green-yellow. The condensation product is filtered off and condensed with l-amino- 4-(4'-aminophenylamino)-anthraquinone-2-sulfonic acid in the manner described above.

Example 2 39.3 parts of the secondary condensation product of 1 mol of cyanuric chloride, 1 mol of aniline and 1 mol of 1:3-diaminobenzene-4-sulfonic acid are suspended in 300 parts of water and 25 parts of hydrochloric acid of 30 percent strength, and diazotized at about l0-15 C. with 25 parts by volume of a 4 N-solution of sodium nitrite. To the resulting slightly yellow colored diazo suspension there are added 30 parts of sodium acetate and then there is slowly added at l0-15 C. a solution of 21.5 parts of 1-(2'-chlorophenyl)-3-methyl-S-pyrazolone 6 droxide. When the coupling is finished the precipitated dyestuff is filtered oil and washed with sodium chloride solution of 1% strength.

The product so obtained is stirred in the form of a moist paste with 1000 parts of water at C., and a neutral solution of 40.9 parts of 1-amino-4-(4'-aminophenylamino)-anthraquinone-2-sulfonic acid in 500 parts of water at 60 C. is added. The whole is heated to 90-95 C. After a short time the mixture which is initially alkaline to brilliant yellow paper becomes acid to litmus. The hydrochloric acid formed is neutralized continuously with a dilute solution of sodium carbonate. After stirring the mixture for about 20 hours at 90-95 C. the reaction remains constantly neutral. The condensation is finished. After cooling the mixture ito C., the green dyestiiif formed is salted out with sodium chlo ride solution of 10% strength and filtered off. 1 After drying, there is obtained in good yield a green dyestuff powder. The dyestuff dyes wool from a neurtal or acetic acid bathyellowish pure green tints having good properties of fastness.

In the following table are given in the second column the tints on wool produced by similar dyestuffs obtained byhthe above method by condensing the anthraquinone dyestufl of the formula solrr 7 NEG-NH.

instead of the above-menitoned secondary condensation in 104 parts by volume of a 1 N-solution of sodium hy- 35 product, with those given in the first column of the table.

OKs-CHI /N\ v on, l err-na-c CHr-CH y son: -o

in N=NCH(J-CH; Groom {om- H, mo GH-lifieNH our-ch, I JHI'N N sod! o a in N=N-ono-cm Do.

/N\ NH(I3/ (IIJNH som c (:1 N=N-cH-c -cn, Do.

/N\ NH-o (J-NH son \a I 8 in N=N-oH-- 3-om Do.

NH; I /N\ NH-m lC-NE r w s 01 N=N- Cl1\ C 0 strong bluish 6811. CONH gr Example 3' tion is run into a suspension of 18.4 parts of cyanuric 23.0 parts of l-acetylamino-3-aminobenzene4-sulfonic' at 50 C. by making the reaction neutral to phenolphthalein'. The mixture is filtered and there is obtained in good yield theexpected yellow amino-azo-dyestuff.

parts of the amino-azo-dyestuff so obtained are dischloride in 200 parts of ice and parts of water while stirring well. The temperature is maintained at 10-15 C. by the addition of ice. The whole is stirred for 4 hours at 10-15 C., during which the hydrochloric acid liberated is neutralized by the addition of a 1 N-solution of caustic soda.

40.9 parts of 1-amino-4-(4-a.minophenylamino)-anthraquinone-Z-sulfonic acid are dissolved in 500 parts of water at 50 C. and rendered neutral with caustic soda solution, and added to the suspension of the cyanuric solved in 650 parts of Water at -70 C., and the soluchloride mouocondensate. The whole is heated to 40 C.

faasaoaa.

i.e. about 240 parts of sodiurnchloride, is added, the

Example 4 5.2 parts of the dyestuif of the formula i NET-(I3 (fi-NH- O @SOaNa (JO-NH (31 N= N-.--O

are stirred in 200 parts of water at 70 C. After the addition of a solution, heated at 40 C. of 4.09 parts of 1 amino 4 (4 aminophenylamino) anthraquinone-2-sulfonic acid and 0.4 part of sodium hydroxide in 200 parts of water, the reaction mixture is boiled under reflux for 24 hours, during which the reaction is constantly maintained neutral to litmus by the addition of dilute sodium carbonate solution. After the addi- Example 5 18.5 parts of cyanuric chloride are finely suspended in 600-parts of ice and 200 parts of water. A neutral solution of 18.8 parts of 1:3-diaminobenzener4-sulfonic acid in 400 parts of water is added. The hydrochloric acid liberated is neutralized with 100 parts of a l N-so-" lution of sodium hydroxide in such manner that the pH value does not exceed 6.5. After 15' minutes'at- 0 C:

the condensation is finished. The pH value isadjusted to 8.5 by the addition of a dilute solution of sodium hydroxide, 25 parts of a 4 N-solution of sodium nitrite are added and the solution so obtained is run inth'e course of 15 minutes into 60 parts by volume of a solution containing substantially 30 percent of naphthalene-l-sulfonic acid. The wholeis stirred for 2 hours at 20 C. and 12.8 parts of barbituric acid in 400 parts of water and 200 partsof sodium carbonate solution of 10% strength are run in in the form of a fine stream at 20 C. When the coupling is finished the dyestuif is precipitated with sodium chloride and filtered ofi. It

i 7 is suspended in 1000 parts of water at 20 C., a neutral solution of the disodium salt of 1-amino-4-(4-aminophenylamino)-2:3'-disulfonic acid in 500 parts of water at 60 C. is added, and the condensation is carried out for 24 hours at- 4045 C. at a' pH value of 6.5. The mixture is finally rendered alkaline by the addition of 5 parts of sodium carbonate, and the dyestufl is precipitated by the addition of 10 parts by volume of a saturated solution of sodium chloride, filtered off and g dried.

The dyestufi dyes cellulose fibers from an "alkaline bath containing a salt or by the so-called pad dyeing process and subsequent fixation with alkali fast bluish green tints.

Example 6 Q A solution of 0.02 mol of the disodium salt of 1- tion of 60 parts of a saturated solution of sodium chlo 2:3'-disulfonic acid in 400 cc. of cold water is cooled to 0 C., and then a solution of 3.8 grams of cyanuric chloride in 20 cc. of acetone is added. The mixture is stirred for 30-60 minutes at 05 C., ,during which the acid liberated is continuously neutralized by the addition of a dilute solution of sodium hydroxide. When the condensation is finished a neutral solution: of 0.02

, mol of the dyestuff of the formula C= HzN SOaNa in 400 cc. of water is added. The mixture is warmed to 35 C. and stirred for about 7 hours at 3540 C., during which the acid liberated is continuously neutralized by the addition of a dilute solution of sodium hydroxide. The green dyestufi so obtained is precipitated by the addition of sodium chloride and filtereduoif. When dry it is a dark powder which dissolves in water with a green coloration and dyes cellulose by the dyeing process described in Example 8 green tints which are very fast to washing and light.

The yellow dyestufli of the above formula used as intermediate product can be prepared in known manner by diazotizing 4-acetylamino-2-aminobenzene-l-sulfonio acid, coupling the diazo compound with 3-methyl-pyrazolone-(S), and then hydrolysing the acetylamino group with dilute hydrochloric acid. 1

The above dy'estufi, which dyes cellulose green tints, can also be prepared by first reacting 1 mol of the yellow dyestutf of the above formula with 1 mol of cyanuric chloride'and then condensing the yellow primary condensation product so obtained with 1 mol of l-amino- 4 (4 aminophenylamino) anthraquinone 2:3 d1.

Tint

Green.

Hm N=N-0/ smH Blue Component OaH sulfonic acid. The yellow primary condensation prodnot can also be prepared by diazotizing the condensation product of 1 mol of 1:3-diaminobenzene-4-sulfonic acid with 1 mol of cyanuric chloride and then coupling the diazo' compound with S-methyl-S-pyrazolone.

1 SOIH NE NH:

N-N-G SOIH BIN

NH NH:

NH NH:

SOsH

NH -Nn= SOaH NH NH:

Blue Component CI) NH: @4093 0 NHa H l ms 0 =11 O NH NH5 SOaH 9 N135 m l I O NE NH! 1 TH NH:

NH: m som I l O NH NH:

Ci) NH: m-som NH NH:

O NH:

Green.

No. Blue Component Yellow Component Tint 01 H l O NH: V II I V /C-N -s0,n s2 SOsH HQN N=N--C/ oats.

H: SOsH Am I NHONROH,

01 on O NH: ([1 l! l -N 01H 7 as -so,H HQN N=NC l Do.

! NEG-Nubia r or 0 NH OH H l a 7 bN SO=H a4 SO:H mN N=N C I Do.

C=N notssort; 1

CH: NEG-News,

II I

sons HIN Do.

NE NH:

Example 7 A similar good result is obtained by using, instead of the 2 parts of the dyestuff obtained as described in Example 1 are dissolved in 4000 parts of water, 10 parts of crystalline sodium sulfate are added to the dyebath, and 100 parts of wool are entered at 40--50 C; There are then added 2 parts of acetic acid of 40 percent strength,

cotton fabric, a -'fabric of staple fibers of regenerated 5 cellulose.

the bath is raised to the boil in the course of 9% hour,

and dyeing is carried on for /1 hour at that temperature. After rinsing and drying the material, there is obtained a green dyeing which is very fast to washing and fulling.

The same result is obtained when the dyebath contains no acetic acid or when superpolyamide fibers are dyed, instead of wool.

Example 8 V 1 part of the dyestuft obtained as'described in the first paragraph of Example 6, is mixed with 9 parts of urea and dissolved in 100 parts of Water. A cotton fabric is impregnated with the resulting solution at 80 C. on the foulard, and then the excess liquid is squeezed off until the material retains 75% of its Weight of dyestulf solution. w

The impregnated fabric is dried, then impregnated at room temperature in a solution which contains, per liter, 10 grams of sodium hydroxide and 300 grams of sodium chloride, the fabric is squeezed until it retains 75 percent of its weight of liquid, and is then steamed for seconds at 100-101 C. It is then rinsed, treated in a solution of sodium bicarbonate of 0.5 percent strength, rinsed again, soaped for A; hour in a solution of 0.3 percent strength of an ion-free detergent at the boil, rinsed and dried.

There is obtained a dyeing which is fixed fast to boiling,

A similar good result is also obtained by carrying out the impregnation with the dyestufi solution at a temperature of 30 C. instead of C.

What is claimed is:

1. A dyestuff which in its free acid state-corresponds to the general formula wherein R represents a benzene radical and R; represents a benzene sulfonic acid radical with the sulfonic acid group in ortho position to the azo nitrogen, X represents a nitrogen bridge bound to R in meta-position to the azo linkage, Y represents the radical of a heterocyclic ketornethylene compound containing two nitrogen atoms as hetero atoms and being bound to the 520 linkage in a position vicinal to a ketogroup and A represents a member selected from the group consisting of a chlorine atom, an H N-group, a methoxy group, a phenoxy group and the radical of an organic monoamine having at most 7 carbon atoms and being bound through its amino group, and n represents a whole number up to 3.

2 1 22 2-; A dyestufii'wliich-i'n-itsfiee acidstate= corresponds wherein Y" represents a member ar the group consisting the fOYmula of the radical of barbituric acid and the radicaP ofa 3rf methyl-S-pyrazolone bound to the azo linkage in the 4- 2 so H 5 position, A represents a lower hydrocarbon radical containing at most 6 carbon atoms and selected" from the group consisting of lower alkyl groups and mononuclear 00 six-membered carbocyclic'rings, and n is atwhole' num- 10 her up to 2, A and Y being free-from: sulfonic acid NH-i (J-NH- N=NY groups 4. The dyestulf-which in its free acid state corresponds soar to the. formula NH: 00 om Cl CIh HaC-N-li H: 01 00 NH /(|J\ C 1 If N' (JO-N NH-ti NH N=N-o' Q \C=N -SO|H CH:

wherein Z represents a member selected from the. group 5. The dyestuff which in its free acid state corresponds consisting of. asulfonic acid group and a hydrogen; atom to the formula:

oo-N--- N=N-CH 01 -so H C:

a (BB:

and Y represents a member of the group consisting of 6. The dyestuif which in its free acid state corresponds the radical of barbituric acid and the radical of a 3- to the formula Cl c0 NH- SOaH 1 r C0NH NH--o (E-NH- N=NCH co N C0-N son:

methyl-S-pyrazolone bound to the azo linkage in the 4- position. 7. The dyestuff which in its free acid state corresponds 3. A dyestufi which in its free acid state corresponds to the formula to the formula NE; NH, 00 co soni smn A" n-lHh-l Cl c6 7 06 NE- 0 NH- rI N r r ITI CO-NH NH-o d-NH- N=N--Y NH-C\ /C-NH- N=N-c l N S0|H OIH i N 1 8. vThe dyestuif which in its free acid state corresponds 10. A;dyestufi which its free. acidstate corresponds ot e mu a I o0 son;

to the formula 30:11 2 a V where n Z represents a member selected from the group wherein Z represents a member selected from the group 30 consisting of-a sulfonic acid group and a hydrogen atom,

consisting a sulfonic acid group and a hydrogen atom, and Y represents the radical of a heterocyclic ketomethylone compound containing two nitrogen atoms as hetero,

A represents lower alkylamino bound through its amino group, and Y represents the radical of a heterocyclic ketomethylene compound containing two nitrogen atoms atoms and being bound to the azo linkage in a position as hetero atoms and being bound to the azo linkage in a vicinal to a keto group.

35 position vicinal to a keto group.

References Cited" in the file 'of this patent UNITED STATES PATENTS 2,795,576 Fasciati June 11, 1957 2,853,482 Gunot Sept. 23, 1958 FOREIGN PATENTS Great Britain Nov. 16, 195 5 

1. A DYESTUFF WHICH IN ITS FREE ACID STATE CORRESPONDS TO THE GENERAL FORMULA 